Metal-Organic Frameworks E-Book

• Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1002

Veröffentlichungsjahr: 2018

Beschreibung

Focusing on applications in separation, adsorption and catalysis, this handbook underlines the importance of this hot and exciting topic. It provides an excellent insight into the synthesis and modification of MOFs, their synthesis on an industrial scale, their use as CO2 and chemical warfare adsorbers, and the role of defects in catalysis. In addition, the authors treat such new aspects as biocatalysis and applications in photocatalysis and optoelectronic devices.

Leseprobe

Table of Contents

Cover

Title page

Copyright

Preface

Chapter 1: The Stability of Metal–Organic Frameworks

1.1 Introduction

1.2 Chemical Stability

1.3 Thermal Stability

1.4 Mechanical Stability

1.5 Concluding Remarks

Acknowledgments

References

Chapter 2: Tuning the Properties of Metal–Organic Frameworks by Post‐synthetic Modification

2.1 Introduction

2.2 Post‐synthetic Modification Reactions

2.3 PSM for Enhanced Gas Adsorption and Separation

2.4 PSM for Catalysis

2.5 PSM for Sequestration and Solution Phase Separations

2.6 PSM for Biomedical Applications

2.7 Post‐synthetic Cross‐Linking of Ligands in MOF Materials

2.8 Conclusions

References

Chapter 3: Synthesis of MOFs at the Industrial Scale

3.1 Introduction

3.2 MOF Patents

from Academia versus the Industrial Approach

3.3 Industrial Approach to MOF Scale‐up

3.4 Examples of Scaled‐up MOFs

3.5 Industrial Synthetic Routes toward MOFs

3.6 Concluding Remarks

Acknowledgments

References

Chapter 4: From Layered MOFs to Structuring at the Meso‐/Macroscopic Scale

4.1 Introduction

4.2 Designing Bidimensional Networks

4.3 Methodological Notes Regarding Characterization of 2D Materials

4.4 Preparation and Characterization

4.5 Properties and Potential Applications

Acknowledgments

References

Chapter 5: Application of Metal–Organic Frameworks (MOFs) for CO

2

Separation

5.1 Introduction

5.2 Factors Influencing the Applicability of MOFs for CO

2

Capture

5.3 Current Trends in CO

2

Separation Using MOFs

5.4 Conclusion and Perspective

References

Chapter 6: Current Status of Porous Metal–Organic Frameworks for Methane Storage

6.1 Introduction

6.2 Requirements for MOFs as ANG Adsorbents

6.3 Brief History of MOF Materials

for Methane Storage

6.4 The Factors Influencing Methane Adsorption

6.5 Several Classes of MOFs for Methane Storage

6.6 Conclusion and Outlook

References

Chapter 7: MOFs for the Capture and Degradation of Chemical Warfare Agents

7.1 Introduction to Chemical Warfare Agents (CWAs)

7.2 Adsorption of CWAs

7.3 Catalytic Degradation of CWAs

7.4 MOF Advanced Materials for Protection against CWAs

7.5 Summary and Future Prospects

References

Chapter 8: Membranes Based on MOFs

8.1 Introduction

Acknowledgments

References

Chapter 9: Composites of Metal–Organic Frameworks (MOFs): Synthesis and Applications in Separation and Catalysis

9.1 Introduction

9.2 Synthesis of MOF Composites

9.3 Applications of MOF Composites in Catalysis and Separation

9.4 Conclusions

References

Chapter 10: Tuning of Metal–Organic Frameworks by Pre‐ and Post‐synthetic Functionalization for Catalysis and Separations

10.1 Introduction

10.2 Pre‐synthetic Functionalization

10.3 Type 1 or Physical Impregnation

10.5 Type 3 or

In Situ

Reaction

10.6 Type 4 or Ligand Replacement

10.7 Type 5 or Metal Addition

10.8 Conclusions

References

Chapter 11: Role of Defects in Catalysis

11.1 Introduction

11.2 Definition of MOF Defect

11.3 Classification of MOF Defects

11.4 Formation of MOF Defects

11.5 Characterization of Defects

11.6 The Role of Defect in Catalysis

11.7 Conclusions and Perspectives

Acknowledgment

References

Chapter 12: MOFs as Heterogeneous Catalysts in Liquid Phase Reactions

12.1 Introduction

12.2 Synthesis of Different Classes of Organic Compounds over MOFs

12.3 Specific Aspects of Catalysis by MOFs

12.4 Concluding Remarks and Future Prospects

References

Chapter 13: Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis

13.1 Introduction

13.2 Nanoparticles in MOFs for Gas and Liquid Phase Oxidation Catalysis

13.3 Nanoparticles in MOFs in Hydrogenation Reactions

13.4 Nanoparticles in MOFs in Dehydrogenation Reactions

13.5 Nanoparticles in MOFs in C─C Cross‐Coupling Reactions

13.6 The Use of Nanoparticles in MOFs in Tandem Reactions

13.7 Conclusions and Outlook

References

Chapter 14: MOFs as Supports of Enzymes in Biocatalysis

14.1 Introduction

14.2 MOFs as Biomimetic Catalysts

14.3 Enzyme Immobilization Strategies

14.4 Biocatalytic Reactions Using Enzyme–MOFs

14.5 Conclusions and Perspectives

Acknowledgments

References

Chapter 15: MOFs as Photocatalysts

15.1 Introduction

15.2 Properties of MOFs

15.3 Photophysical Pathways

15.4 Photocatalytic H

2

Evolution

15.5 Photocatalytic CO

2

Reduction

15.6 Photooxidation Reactions

15.7 Photocatalysis for Pollutant Degradation

15.8 Summary and Future Prospects

Acknowledgements

References

Index

End User License Agreement

List of Illustrations

Chapter 1: The Stability of Metal–Organic Frameworks

Figure 1.1 Selected M(III and IV)‐carboxylate inorganic building units and MOFs. (a) M(III)‐oxo‐trimer, (b) 12‐connected Zr(IV)‐hexanuclear oxo‐cluster, (c) M(III) chains, and (d) Zr(IV) chains found in MIL‐140 (i). Crystalline structures of (e) MIL‐53 [23], (f) MIL‐100 [32], (g) MIL‐127 or

soc

‐MOF [33], (h) UiO‐66 [34], and (i) MIL‐140A [35]. Color code: M(III) = Fe

3+

, Al

3+

, etc., dark gray; Zr, violet; C, gray; N, blue; O, red. The cages are represented by colored spheres. Hydrogen atoms are not represented for the sake of clarity.

Figure 1.2 Selected M(II)‐azolate inorganic building units. Pyrazolate (a) Ni‐tetranuclear and (b) Ni‐octanuclear building units. Crystalline structures of (c) ZIF‐8 [93], (d) Ni(BTP) [94], (e)

fcu

‐Ni(DP) [95], and (f) PCN‐601 [96]. Color code: Ni, green; Zn, cyan; C, gray; N, blue; O, red. The cages are represented by colored spheres. Hydrogen atoms are not represented for the sake of clarity.

Figure 1.3 Crystalline structures of two highly stable chain‐based MOFs: (a) Fe

2

(BDP)

3

[105] and (b) MIL‐163 [106]. Color code: Fe, yellow; Zr, violet; C, gray; N, blue; O, red. Hydrogen atoms are not represented for the sake of clarity.

Figure 1.4 Illustration of PDMS coating on the surface of MOFs and the improvement of moisture/water resistance.

Chapter 2: Tuning the Properties of Metal–Organic Frameworks by Post‐synthetic Modification

Figure 2.1 The four main classes

of post‐synthetic modification reaction involve (a) covalent modification of a linker, (b) exchange of linker ligands, (c) exchange of terminal ligands, and (d) exchange of metal centers.

Figure 2.2 The structures of the tcpb and dped linkers.

Scheme 2.1 Modification of MIL‐101

(Cr) by coordination of amines to the chromium centers.

Scheme 2.2 Suggested mechanism for photocatalytic reductions

by UiO‐66(Ti/Zr)‐NH

2

[51]. Triethanolamine

(TEOA) serves as electron and proton source.

Scheme 2.3 Attachment of a metal site to a copper‐based MOF via a node‐based linker.

Scheme 2.4 Immobilization of an iridium catalyst on UiO‐66‐NH

2

via PSM.

Scheme 2.5 Introduction of acid and base sites into MIL‐101(Cr) via tandem PSM.

Figure 2.3 The structures of the Safranin T (ST) and Crystal Violet (CV) dyes.

Scheme 2.6 Post‐synthetic modification of bdc‐NH

2

in [Fe

3

OCl(H

2

O)

2

(bdc)

3–

x

(bdc‐NH

2

)

x

] with the bioactive molecules ESCP and Br‐BIODIPY.

Figure 2.4 Use of a cross‐linked bdc ligand to obtain an isostructural material to IRMOF‐1.

Scheme 2.7 Cross‐linking of ligand‐derived pendant alcohol groups using di(

tert

‐butyl)silyl ditriflate to yield a PSM‐induced cross‐linked network.

Scheme 2.8 Achieving higher topologies in coordination frameworks by post‐synthetic photodimerization of styryl‐functionalized ligands.

Figure 2.5 Examples of MOFs converted by

in situ

cross‐linking and digestion to polymer gel species.

Chapter 3: Synthesis of MOFs at the Industrial Scale

Scheme 3.1 Schematic representation

of the industrial‐scale synthesis of MOFs and CPs with emphasis on the important parameters to have in consideration.

Figure 3.1 100 L pilot‐scale reactor (Regional Innovation Center for Industrialization of Advanced Chemical Materials, Hanbat National University) used for the preparation of UiO‐66.

Figure 3.2 Schematic representation of the electrochemical cell used in the preparation of MOFs and CPs using the electrochemical synthesis.

Figure 3.3 Cell used in the electrochemical synthesis of HKUST‐1, depicting the Cu‐plates as the electrode.

Figure 3.4 Schematic representation of a continuous flow apparatus.

Chapter 4: From Layered MOFs to Structuring at the Meso‐/Macroscopic Scale

Figure 4.1 Some of the most simple and representative bidimensional networks for MOFs.

Figure 4.2 (a) Representation of the MOF structure indicating its pore size. (b) High‐resolution transmission electron microscopy (HRTEM) image of the MOF. (c) (HAADF) images taken in STEM mode of the MOF showing the pore dimension. (d) Reconstructed 3D reciprocal lattice from the RED data showing the reciprocal lattice along

c

*, perpendicular to the MOF nanosheet (TEM image in the inset).

Figure 4.3 (a) Overview STM image of large extended regular domains formed by TPA‐Fe (TPA = terephthalic acid) coordination networks. (b) High‐resolution image of 2D polymer Fe‐TDA (TDA = 4,1′,4′,1′′‐terphenyl‐1,4′′‐dicarboxylic acid) open network with rectangular nanocavities. Arrows on the images indicate the high‐symmetry [011] direction of the Cu(100) substrate; positioning of molecular backbone and ligands are marked; Fe atoms are shown as blue spheres. (c) Ladder‐type MOFs account for linear arrangements of single C

60

(yellow spheres) with preferential occupation of larger cavities available. (d) C

60

‐fullerene accommodation in cavities of the network.

Figure 4.4 Fully reticulated nanoporous Fe‐diterephthalate grid assembled on a Cu(100) substrate. (a) Constant current mode scanning tunneling microscopy image showing the R‐isomer comprising a (6 × 4) unit cell (image size 40 × 30 Å

2

). The arrangement of the tpa backbone indicates that a given molecule is engaged in either two bidentate or four unidentate carboxylate bonds to the diiron centers. (b) STM image simulation showing contours of constant LDOS at the sample Fermi level derived from the DFT model of the optimized structural arrangement depicted in model (c).

Figure 4.5 (a) Structure of a single layer of NAFS‐1 viewed along the

c

axis. The pyridine molecules, which are axially coordinated to Co(II) and Cu(II) metal centers to interconnect neighboring nanosheets via π−π stacking, have been omitted for clarity. (b) High‐resolution XPS spectra for a set of films and the reference CoTCPP complex showing the Cu 2p and Co 2p regions. The Cu/Co ratio remains almost constant and is consistent with the theoretical value (dashed gray line) for all transfers. (c) IRRAS spectra after successive growth cycles. The inset shows the maximum absorbance of the most intense peak, ν(COO

asym

) at 1620 cm

−1

, against the number of transfers. Data have been fitted to a linear model (black line). (d) UV–Vis absorption spectra after successive transfer cycles. Dashed light blue line stands for the theoretical maximum absorbance of the Soret band for a NAFS‐1 monolayer. The inset shows the maximum absorbance of the Soret band against the number of transfers. Data have been fitted to a linear regime (black line).

Figure 4.6 (a) Representation of a two‐dimensional monolayer obtained from hexafunctional terpyridine (tpy)‐based D

6h

‐symmetric monomer, held together by Fe(II). Layer thickness (h ≈ 8 Å). (b) Tapping‐mode AFM image with height profile measured along the white line. (c) TEM image after horizontal transfer from top onto a Cu grid with 20 × 20 µm

2

sized holes.

Figure 4.7 (a) Characterization of S1(Zn

2+

) before and after transmetalation. Photographs of (b) fluorescent monolayer sheet S1(Zn

2+

) on quartz (3.3 cm × 1.4 cm), (c) dipping procedure to perform transmetalation, and (d) the sheet after 1 h partial exposure to a 10 mmol L

−1

(NH

4

)

2

Fe(SO

4

)

2

solution in water. (e) UV–Vis and fluorescence spectra of the starting sheet S1 (Zn

2+

) and UV–Vis spectrum of the product sheet. (f) Raman spectra of the starting and product sheet on thin borosilicate glass slides in transmission mode.

Figure 4.8 (a) Synthesis and characterization of nickel bis(dithiolene) complex. (b) Schematic illustration and chemical structure of monolayer nickel bis(dithiolene) complex nanosheet. (c,d) Phase and topological AFM images showing sheets on HOPG and a characteristic height profile of a single layer. (e) STM image of sheets on HOPG showing a hexagonal pattern.

Figure 4.9 (a) Synthesis of a 2DSP single‐layer sheet composed of triphenylene‐fused nickel bis(dithiolene) complexes by using the LB method at an air/water interface. Morphological characterization of THTNi 2DSP layers after vertical transfer onto 300 nm SiO

2

/Si wafers. (b) UV–Vis spectra of THT monomers (dashed line), THTNa monomers (dotted line), and THTNi 2DSP single‐layer sheet (solid line) on quartz wafers. (c) UV–Vis spectral change with controlled growth of the thickness from one to six layers on a quartz wafer. Inset: Linear relationship between the absorbance at 315 nm and the layer number. (c) SEM image showing single‐layer sheet. Scale bar: 10 mm. (d) Tapping‐mode AFM height image and the corresponding cross‐sectional analysis demonstrating a single‐layer sheet measuring approximately 0.7 nm in thickness.

Figure 4.10 (a–c) Surface analysis of Co(II) tetracarboxylate porphyrin–Cu(II) multilayer thin films deposited on ferromagnetic permalloy. AFM topography images of 1, 5, and 10 transfers show the progressive increase in coverage and roughness of the films. (d) Evolution of the contact angle of the films with the number of transfers that reaches a stable value (dashed line) right after two transfers. This suggests the formation of smooth, homogeneous films from this point on. (e) Roughness of the film versus the number of transfers showing a steady increase in roughness from about 0.4 to 1.9 nm after 10 transfers (data have been fitted to a linear model). (f) AFM image of a manually scratched 10‐transfer film. (g) Height distribution of the above image showing a thickness value of 10.2 nm. (h) Evolution of film thickness with the number of transfers.

Figure 4.11 Synthesis and microscopic analysis of multilayer N1. (a) Schematic illustration and photographs of the liquid–liquid interfacial synthesis and multilayer N1 transferred onto an ITO substrate. Scale bars, 5 and 1 mm, respectively. (b) Optical microscopic image on an ITO substrate. Scale bar, 50 mm. (c) (FE‐SEM) image on HMDS/Si(111). Scale bar, 20 mm. (d) AFM image on HMDS/Si(111) and its cross‐sectional analysis along the magenta line. Scale bar, 5 mm. (e) Control of the thickness based on the concentration of the organic ligand in the liquid–liquid interfacial synthesis. The inset shows a close‐up of the low concentration region. (f) UV–Vis spectra of the ligand and metal fragment (initial building blocks) in toluene and few‐layer N1 on a quartz substrate. (g) Spectral change on stepwise depositions of single‐layer N1 on a quartz substrate (inset showing the linear relationship between the absorbance at 500 nm and the number of deposition processes).

Figure 4.12 (a) 3D crystalline structure of CuBDC MOF. The insets on the right‐hand side show views along the

b

(top) and

c

(bottom) crystallographic axes. (b) SEM micrograph of bulk‐type CuBDC MOF crystals. (c) Picture showing the spatial arrangement of different liquid layers during the synthesis of CuBDC MOF nanosheets. Layers labeled as (i), (ii), and (iii) correspond to a benzene‐1,4‐dicarboxylic acid (BDCA) solution, the solvent spacer layer, and the solution of Cu

2+

ions, respectively. Schematic representation of the concentration gradients established for Cu

2+

and linker precursors at the spacer layer is also depicted on the right. (d) X‐ray diractograms (CuKα radiation) for the bulk‐type and nanosheet CuBDC MOF. (e,f) SEM micrograph and AFM image (with corresponding height profiles), respectively, for CuBDC MOF nanosheets.

Figure 4.13 (a) View of a single layer of [Cu

2

Br(IN)

2

]

n

. (b) Superposition of layers along the

a

axis. (c) AFM topography image of [Cu

2

Br(IN)

2

]

n

deposited on HOPG. (d) A typical height of profile of a layer.

Figure 4.14 (a) View of a layer of [Cu(μ‐pym

2

S

2

)(μ‐Cl)]

n

n

H

2

O. (b,c) Representative AFM topographies and heights profiles obtained upon drop‐casting adsorption on mica of the suspensions obtained upon treatment of [Cu(μ‐pym

2

S

2

)(μ‐Cl)]

n

n

H

2

O crystals with water at different exposition times: 1 day (b) and 4 days (c).

Figure 4.15 (a,b) Surface rendered views of the FIB‐SEM tomograms for composite membranes containing Cu(BDC) nanosheets (a) and bulk crystals (b) embedded in polyimide. MOF particles are shown in gray. The dimensions of the boxes along the

x

:

y

:

z

directions are 4.9 : 4.9 : 6.6 µm in (a) and 11.2 : 11.2 : 7.6 µm in (b).

Figure 4.16 (a, b) Schematic (a) and optical micrograph (b) of bottom‐gate, bottom‐contact FET based on Cu‐BHT films. (c) Action spectrum for photocurrent generation (dots) and UV–Vis absorption spectrum (line) of bis(dipyrrinato)zinc(II). (d) Anodic current response on irradiation with intermittent 500 nm light of a working electrode with 36‐layer‐thick bis(dipyrrinato)zinc(II) film.

Figure 4.17 (a) Formation and structure of the hafnium‐based MOF. (b) Preparation of catalyst by doping the Hf‐based MOF structure with 4′‐(4‐benzoate)‐(2,2′,2″‐terpyridine)‐5,5″‐dicarboxilate (TPY) ligand and scheme of the catalyzed reaction.

Chapter 5: Application of Metal–Organic Frameworks (MOFs) for CO

2

Separation

Figure 5.1 Comparison between the experimental results of Herm

et al

. [43] (open), Queen

et al

. [44] (yellow), Yu

et al

. [45] (orange), and Dietzel

et al

. [46] (brown) and simulation results using the developed polarizable force field (black), the UFF force field (blue), and the DFT‐derived nonpolarizable force field of Mercado

et al

. [47] (green) for CO

2

in Mg‐MOF‐74. (a) Adsorption isotherm at 298 K (Herm

et al

. [43] 313 K); (b) heat of adsorption as a function of uptake.

Figure 5.2 Description of the ligand H2PDC, the SBUs, and the 3D structures in (a) Cu

2

(CO

2

)

4

paddlewheel SBU and Cu

2

I

2

dimer SBU, (b) Cu

2

(CO

2

)

4

paddlewheel SBU and Cu

4

I

4

SBU, and (c) Cu

2

(CO

2

)

4

paddlewheel SBU, Cu

2

I

2

dimer SBU, and Cu

2

(CO

2

)

4

SBU with the optical photos (Cu, blue; N, green; C, gray; O, red; I, brown).

Figure 5.3 Single‐crystal X‐ray structure of ZIF‐202. (a) Combining tetrahedral ZnN

4

, linear CuN

2

, and imidazole led to (b) ZIF‐202. (c) The crystal structure of ZIF‐202 adopts the sql layered topology. Atom colors: Zn, blue polyhedra; Cu, red; C, black; N, green; all H atoms are omitted for clarity.

Figure 5.4 Preparation of amine‐functionalized Mg

2

(dondc)

using three different diamines.

Figure 5.5 CO

2

adsorption mechanisms on den‐Mg(dobpdc) producing ammonium carbamates in (a) 1 : 1 ratio of CO

2

to amine and (b) 1 : 2 ratio of CO

2

to amine. Each mechanism could include four combination modes depending on the relative positioning of methyl side groups.

Figure 5.6 Percentage enhancement of the selectivity of the IL/MOF (a,b) and IL/COF (c,d) composites relative to their respective pristine support materials. (a,c) CO

2

/N

2

mixture (CO

2

:N

2

 = 15 : 85) at 1 bar. (b,d) CO

2

/CH

4

mixture (CO

2

:CH

4

 = 10 : 90) at 10 bar.

Figure 5.7 Screening of CO

2

adsorption on 43 MOFs under wet and dry conditions. The zones correspond to the severity of water impacts on CO

2

capacity from (a) less severe to (d) high severe effects.

Chapter 6: Current Status of Porous Metal–Organic Frameworks for Methane Storage

Figure 6.1 (a) Gravimetric methane uptakes at room temperature versus gravimetric specific surface areas. (b) Volumetric methane uptakes at room temperature versus volumetric specific surface areas. The selected MOFs include HKUST‐1, NiMOF‐74, PCN‐14, UTSA‐20, NU‐125, NU‐111, UTSA‐76, NOTT‐101, MOF‐519, Al‐

soc

‐MOF‐1, Cu‐

tbo

‐MOF‐5, DUT‐49, and MAF‐38.

Figure 6.2 (a) Two different types of cavities in Cu‐

tbo

‐MOF‐5; (b) high‐pressure methane adsorption isotherms of Cu‐

tbo

‐MOF‐5 at three different temperatures; and (c) five major CH

4

adsorption sites in Cu‐

tbo

‐MOF‐5.

Figure 6.3 (a) The crystal structures of five NbO‐type MOFs exhibiting two different types of polyhedral cages; (b) the total volumetric methane adsorption isotherms at 300 K; (c) comparison of the experimental and predicted methane uptakes at room temperature and 35 bar.

Figure 6.4 (a) The molecular structures of the nitrogen‐functionalized organic ligands used to construct the corresponding NbO‐type MOFs; (b) comparison of the total volumetric methane uptakes at 298 K and 65 bar indicating that the incorporating nitrogen sites into NOTT‐101 can improve the methane uptakes; (c) the total volumetric methane uptakes at 298 K and 65 bar of functionalized MOFs constructed from different ratios of pyrimidine‐functionalized and unfunctionalized linkers as a function of the molar ratios of functional pyrimidine ligands; (d) comparison of the rotational barriers of the central rings around the linker backbone in UTSA‐76 and NOTT‐101.

Figure 6.5 The crystal structure of NU‐111 (a) and NU‐125 (b) featuring three types of polyhedral cages; high‐pressure methane adsorption isotherms of NU‐111 (c) and NU‐125 (d) at various temperatures. The experimental and simulated isotherms are presented in solid and broken lines, respectively.

Figure 6.6 (a) Zn

4

O SBUs are connected with organic linkers to form MOF‐950, MOF‐905, and functionalized MOF‐905; (b) total volumetric methane adsorption isotherms at 298 K; (c) the structure of MOF‐950 of

pyr

network; (d) the structure of MOF‐905 of

ith‐d

network exhibiting tetrahedral and octahedral cages.

Figure 6.7 (a) Delivery capacity between 65 and 5.8 bar versus void fraction; (b) deliverable capacity between 65 and 5.8 bar versus volumetric surface area; pink:

fcu

topology; green:

ftw

topology; blue:

scu

topology; red:

csq

topology; (c) comparison of deliverable capacity between 65 and 5.8 bar among isoreticular isomeric MOFs.

Figure 6.8 (a)

pbz

‐MOF‐1

was formed by the combination of Zr

6

clusters with the hexatopic H

6

L ligand, displaying the augment

hxg‐a

net, originally described in the structure of polybenzene (

pbz

); (b) methane adsorption isotherms of

pbz

‐MOF‐1 at 298, 273, and 258 K, up to 80 bar.

Figure 6.9 (a) MOF‐519 and MOF‐520 are formed by combining octanuclear Al(III) clusters with the organic BTB linkers; (b) the structure of MOF‐519; (c) the structure of MOF‐520; (d) the total volumetric methane isotherms of MOF‐519 and MOF‐520 at 298 K. Solid and open symbols represent adsorption and desorption, respectively.

Figure 6.10 (a) The assembly of the trinuclear aluminum(III) MBB [Al

3

(

μ

3

‐O)(H

2

O)

3

(COO)

6

] with the organic ligand H

4

TCPT led to Al‐

soc

‐MOF‐1 of (3,6)‐c derived net

edq

; (b) the total gravimetric methane gravimetric adsorption isotherms of Al‐

soc

‐MOF‐1 at different temperatures.

Figure 6.11 Perspective views of (a) the small octahedral cage and (b) large quasi‐cuboctahedral cage in MAF‐38; (c) high‐pressure methane adsorption isotherms of MAF‐38 at 298 K; (d–f) the primary (green), secondary (black) and ternary methane adsorption sites (orange), as well as the unique supramolecular methane dimer and hexamer, as revealed by computational simulation.

Figure 6.12 (a) The transition between the collapsed phase and the expanded phase triggered by the pressures of methane; total methane adsorption isotherms at various temperatures for (b) Co(bdp) and (c) Fe(bdp); (d) differential enthalpies of methane adsorption for Co(bdp), as determined from variable‐temperature adsorption isotherms (purple line) and three separate microcalorimetry experiments (open symbols); (e) Excess methane adsorption isotherms for Co(bdp) at 298 K with different levels of applied external mechanical pressure, indicated by the inset, color‐coded bulk powder densities, with higher densities corresponding to greater applied mechanical pressure.

Chapter 7: MOFs for the Capture and Degradation of Chemical Warfare Agents

Scheme 7.1 (a) Structure and detoxification pathways of nerve agents

GB and VX and vesicant sulfur mustard (HD). (b) Structure of three nerve agent simulants such as diisopropylfluorophosphate (DIFP), dimethyl methylphosphonate (DMMP), and dimethyl 4‐nitrophenyl phosphate (DMNP) and two sulfur mustard simulants, namely, diethyl sulfide (DES) and 2‐chloroethyl ethyl sulfide (CEES).

Scheme 7.2 Acetylcholinesterase activity

(a) and inhibition of enzymatic activity by nerve agents (b).

Figure 7.1 (a) Crystal structure of highly hydrophobic [Ni

8

(OH)

4

(H

2

O)

2

(CF

3

‐L5)

6

]

n

. (b) Dynamic adsorption profiles of DES streams for [Ni

8

(OH)

4

(H

2

O)

2

(CF

3

‐L5)

6

]

n

as well as for Blücher‐101408 activated carbon at 293 K and 80% RH (

m

 = relative weight increase).

Figure 7.2 (a) Molecular structure of the node of UiO‐66 showing four of the twelve bound carboxylates (left) and the connectivity of the octahedral pore in UiO‐66 (right). X

1

 = X

2

 = H for UiO‐66, X

1

 = NO

2

and X

2

 = H for UiO‐66‐NO

2

, X

1

 = X

2

 = OH for UiO‐66‐(OH)

2

, and X

1

 = NH

2

and X

2

 = H for UiO‐66‐NH

2

. (b) Connectivity of the octahedral pore in UiO‐67. X = H for UiO‐67, X = NH

2

for UiO‐67‐NH

2

, and X = N(CH

3

)

2

for UiO‐67‐NMe

2

. (c) Hydrolysis rate of UiO‐66 (blue circles), UiO‐66‐NO

2

(red triangles), UiO‐66‐(OH)

2

(green squares), and UiO‐66‐NH

2

(pink stars). (d) Hydrolysis rate of UiO‐67 (blue), UiO‐67‐NH

2

(red), and UiO‐67‐NMe

2

(green) at half catalyst loading (0.75 µmol) with respect to UiO‐66.

Figure 7.3 (a) Molecular representations of the NU‐1000 node and linker, (b) MOF topology, and (c) the dehydration of the NU‐1000 node

. Color code: Zr (blue); O (red); C (black); H (white). (d) Reaction conditions for the catalytic decomposition of DMNP using NU‐1000. (e) Percentage conversion to

p

‐nitrophenoxide versus time for the background reaction (black diamonds), NU‐1000 (red circles), and NU‐1000‐dehyd (blue squares). The error bars indicate the standard deviation of three independent catalytic tests. (f) Reaction conditions for the decomposition of GD. (g) Loss of GD versus time monitored via

31

P NMR spectroscopy.

Figure 7.4 (a) Scanning electron microscopy (SEM) image of nanosized PCN‐222/MOF‐545

(free base) (nfb‐1). (b) 3D structure of nfb‐1, constructed from a [Zr

6

(μ

3

‐O)

8

(O)

8

]

8−

node and tetrakis(4‐carboxyphenyl)porphyrin linker (tcpp

4−

). (c) View of Zr

6

nodes containing Zr─OH─Zr units that mimic the (d) Zn─OH─Zn active site in phosphotriesterase. (e) Concept of generating singlet oxygen by the porphyrin moieties in nfb‐1 under LED. Hydrogen atoms are not shown in the structures for clarity. (f) Scheme of the dual action of PCN‐222/MOF‐545 for the simultaneous detoxification of nerve agent and mustard gas simulants by the combined action of Zr

6

nodes and porphyrin linkers, respectively.

Figure 7.5 (a) VPSEM images of silk@[UiO‐66@LiO

t

Bu] composite

. Hydrolytic degradation profiles of DIFP (b), DMMP (c), and CEES (d) catalyzed by silk@[UiO‐66@LiO

t

Bu] composite at room temperature. The dotted lines indicate the effect of [UiO‐66@LiO

t

Bu] filtration in order to prove the heterogeneity of the catalytic process.

Figure 7.6 (a) Photo of a freestanding polyamide‐6@TiO

2

@UiO‐66‐NH

2

nanofiber mat. (b–d) SEM images of polyamide‐6@TiO

2

@UiO‐66‐NH

2

. (e–i) Energy dispersive X‐ray mapping images of polyamide‐6@TiO

2

@UiO‐66‐NH

2

. (j) Catalytic reaction of GD hydrolysis using MOF–nanofiber catalysts. (k) Activity of MOF–nanofiber kebab on GD hydrolysis.

Figure 7.7 Field‐effect DMMP sensing strategy using a UiO‐66‐NH

2

adsorbent film. (a) Representation of UiO‐66‐NH

2

showing the [Zr

6

O

4

(OH)

4

]

12+

inorganic clusters, 2‐aminoterephthalate organic linkers, and a missing linker defect site on the cluster. Atom colors: Zr (purple), O (red), C (gray), and N (green). H atoms are omitted for clarity. (b) Schematic representation of the Kelvin probe configuration used in this study. The MOF film is deposited on a stationary electrode that is electrically connected to an oscillating reference electrode. During sensing experiments, the analyte flows between both electrodes. (c) Schematic representation of suspended gate ChemFET, which is a miniaturized counterpart of the Kelvin probe and a potential real‐world implementation. (d) Freundlich isotherm fit of the CPD response, at 0% and 50% RH. (e) Linearized fit of the CPD response in the range of the AEGL‐2 level for sarin.

Chapter 8: Membranes Based on MOFs

Figure 8.1 Scheme of an MOF structure consisting of metal‐based cluster plus organic linker. The yellow sphere represents the confined space.

Figure 8.2 Scheme of the preparation of MOF/MMMs.

Figure 8.3 SEM image of ZIF‐8/Matrimid membrane showing (a) pure Matrimid, (b) MMM with 10% of ZIF‐8, (c) MMM with 20% of ZIF‐8, and (d) MMM with 30% of ZIF‐8.

Figure 8.4 CO

2

/CH

4

selectivity versus CO

2

permeability of polymer membrane (open symbol) and MOF/polymer membranes (full symbols).

Figure 8.5 Robeson plots for CO

2

/CH

4

and H

2

/N

2

.

Figure 8.6 Permeability of O

2

, CO

2

, and H

2

as a function of ZIF‐8 loading.

Figure 8.7 CO

2

/CH

4

selectivity of MMM for 0%, 10%, 20%, and 30% of filler loading.

Figure 8.8 Schematic representation of the reactive seeding method employed to prepare MIL‐53 membranes on porous alumina, where the support acts as the metal source for the preparation of the seed layer, followed by an

in situ

growth step. The SEM images show the seed layer (left) and the resulting MIL‐53‐Al membrane (right).

Figure 8.9 SEM images of the MOF‐5 membrane: (a) top view, (b) cross section.

Figure 8.10 Comparison of the propylene/propane separation

performance of ZIF‐8 membranes [97] with those of other membranes reported in the literature. Triangle: Carbon membrane (Refs [6–8] in [97]). Circle: zeolite membrane (Ref. [5] in [97]). Rectangle: polymer membrane (Ref. [3] in [97]). Pentagon: ZIF‐8 membrane (Ref. [31] in [97]). Hexagon: ZIF‐8 mixed matrix membrane (Ref. [31] in [97]). Star: ZIF‐8 membrane [97].

Figure 8.11 Robeson plot for CO

2

/CH

4

and H

2

/N

2

gas couples

for thin‐film MOF‐based membranes. (See Tables 8.3 and 8.4 for correspondent references).

Figure 8.12 Scheme of the effects of water vapor and other gas impurities in flue gas on CO

2

/N

2

separation using ZIF‐68.

Figure 8.13 Comparison between experimental and simulated pure‐gas permeability values of H

2

, CH

4

, CO

2

, and N

2

in IRMOF‐1/Matrimid membrane at 35 °C and 2 atm. Open and full symbols are the simulated permeability values evaluated with Maxwell and Bruggeman models, respectively.

Chapter 9: Composites of Metal–Organic Frameworks (MOFs): Synthesis and Applications in Separation and Catalysis

Figure 9.1  Preparation of MWCNT@JUC‐32 composite.

Figure 9.2  Synthesis of ZIF‐8@GO composite.

Figure 9.3  The pretreatment of the ceramic foam support

and the synthesis of the MOF thin films.

Figure 9.4  The preparation of MOF‐101(Al)@Al

2

O

3

composites.

Figure 9.5  Synthesis

MOP–MNP composites and classifications.

Figure 9.6  Scheme for the synthesis of AuNiNPs@MOF by double solvent method incorporating the reduction reaction with NaBH

4

.

Figure 9.7  Scheme for the one‐step synthesis process

of Fe

2

O

3

@MOF.

Figure 9.8  Scheme for the formation of CPO‐27‐Mg/TiO

2

nanocomposite by the hydrothermal process.

Figure 9.9  Scheme for the synthesis of Cu

x

O NPs@ZIF‐8 through facile pyrolysis of a nanocrystalline nHKUST‐1@ZIF‐8.

Figure 9.10  Detailed scheme for the synthesis of OMS@Pd‐ZnMOF‐

x

.

Chapter 10: Tuning of Metal–Organic Frameworks by Pre‐ and Post‐synthetic Functionalization for Catalysis and Separations

Figure 10.1 Terephthalate ligands commonly used for pre‐synthetic functionalization

of MOF structures.

Figure 10.2 Chemical structure of naproxen (a), ibuprofen (b), and oxybenzone (c), pharmaceutical compounds that have been targeted for adsorption‐utilizing functionalized MOFs [57].

Figure 10.3 Terephthalate ligands functionalized with various moieties and the resulting MOFs created.

Figure 10.4 Functionalization route utilized by Schneemann

et al

. with (a) side view of framework cavity, (b) single cavity showing solvated state (lp) and activated state (np), and (c) linker chemical structures used [79].

Figure 10.5 Biphenyl benzene dicarboxylic acid ligands

with SO

2

functional groups as used by Couck

et al

.

Figure 10.6 Photoresponsive SURMOF

created by Wang

et al

. showing the light‐initiated pore opening/closing they proposed [83].

Figure 10.7 Knoevenagel condensation

attempted by Gascon

et al

. [49].

Figure 10.8 Grignard reaction

for Hg adsorption proposed by Zhang

et al

. [69].

Figure 10.9 Removal of mercury efficiency for each MOF tested by Zhang

et al

. [69].

Figure 10.10 Carbon capture and efficiency on ZIF‐8 materials [104].

Figure 10.11 Nanoparticle introduction method utilized on ZIF‐67 by Li

et al

. [109].

Figure 10.12 Mg/DOBDC pore space with (a) no functional groups, (b) 1 functional group, (c) 3, (d) 6, and (e) 18 ethylenediamine functional groups per cell.

Figure 10.13 Coumarin grafted onto Zn‐MOF‐74 by Zhang

et al

. for the removal of U(VI) ions [128].

Figure 10.14 Mo(VI) complex added to the COMOC‐4 structure by Leus

et al

. [131].

Figure 10.15 Method to create novel MOFs via deprotection‐style functional group photodegradation as shown by Allen and Cohen [85].

Figure 10.16 Method to deaggregate MOFs via polymer branching as shown by Xie

et al

. [134]

Figure 10.17 Schematic of the ship‐in‐bottle approach to introduce ionic liquids to MOFs as shown by Khan

et al

. [135].

Figure 10.18 Method used by Sun

et al

. to create ZIF‐8 with superhydrophobic and oleophobic functional groups [137].

Figure 10.19 Schematic proposed by Choe

et al

. for the creation of secondary ligand species into 2D grid MOFs [138]. Shown at (A) is (a) schematic of the layers and (b) of pillaring method. Shown at (B) is (a) replacement of PPF‐18 to form PPF‐27 and (b) of PPF‐20 to form PPF‐4.

Figure 10.20 Transmetalation

routes attempted by Song

et al

. [14].

Figure 10.21 Method utilized by Li

et al

. to introduce aluminum onto sulfur groups within the MIL‐101 structure [158].

Figure 10.22 Schematic of the MIL‐101 pore system functionalized with a ruthenium complex by Beloqui Redondo

et al

. Green, aluminum; red, oxygen; gray, carbon; pink, phosphorus; blue, nitrogen; orange, ruthenium; light green, chloride. Shown are (a) local pore system, (b) local metal node environment, and (c) cage functionalization [159].

Chapter 11: Role of Defects in Catalysis

Figure 11.1 The definition of defects: the missing and incorrectly located atoms generate vacancies and dislocations in materials [19].

Figure 11.2 AFM amplitude images of {111} facets of HKUST‐1, showing (a) a double‐growth spiral, (b) merging single‐ and multiple‐growth spirals, and (c) growth spirals overlaid with fractures primarily in the <110> directions [27].

Figure 11.3 SEM images of MOF‐5 samples synthesized by varying microwave irradiation times [26].

Figure 11.4 AFM snapshots of the desolvation sequence. Scan area 100 × 100 µm

2

. Several macrosteps 100–300 nm high running perpendicular to [010] are evident. (a) 110 min: the first cracks 1.5 µm wide orthogonal to [010] appear. (b) 170 min: cracks continue to enlarge and small, misaligned blocks appear. (c) 460 min: main cracks are now 4 µm wide and intercalated with smaller blocks. (d) 26 h: a partial healing of the crystalline surface by exposure to water vapor for a few hours is evident [25].

Figure 11.5 Illustrations of (a) the perfect MOFs, (b) the heterogeneous MOFs with an isostructural mixed linker (IML), and the defective MOFs with a heterostructural mixed linker (HML) by (c) the large mixed linker (LML) and (d) the truncated mixed linker (TML) approaches for framework functionalization [19, 46].

Figure 11.6 (a) Synthesis of BTB‐incorporated MOF‐5 crystals by addition of H

3

BTB to the reaction mixture of H

2

BDC and Zn–(NO

3

)

2

·6H

2

O. (b) Photographs of crystals showing the dependence of the morphology upon the percentage of H

3

BTB in the feed (scale bar: 100 µm). Needle‐shaped UMCM‐1 crystals appear above 10 mol% H

3

BTB [7].

Figure 11.7 Schematic illustration of the ligand truncation method. Scaffold represents one of the pores of PCN‐125 with R‐TPTC (a) and with TPTC and R‐isoph (b) [3].

Figure 11.8 Pore structures of MOF‐5, spng‐MOF‐5, and pmg‐MOF‐5 revealed by SEM observation of their crystal surface and interior (scale bars, green 50 µm, red 1 µm, blue 500 nm) [54].

Figure 11.9 Proposed acid activation of the Fe

3

‐μ‐oxo cluster by a protonic acid. A new CUS is opened in one iron octahedron (yellow square). Color code: black is the carboxylate C atom; red is the central oxo anion [34].

Figure 11.10 TGA curves of UiO‐66 samples from different synthesis batches, indicating the presence of linker vacancies. The theoretical weight loss for a fully coordinated UiO‐66 is indicated by the bold vertical arrow between the two horizontal lines [40].

Figure 11.11 Thermogravimetric measurements of HKUST‐1 with 0, 10, 30, and 50 mol% PyDC [13].

Figure 11.12 Schematic Prussian blue (PB) structures with lattice defects in the form of missing [Fe

II

(CN)

6

]

4−

moieties, where Cs

+

ions are trapped by chemical adsorption [57].

Figure 11.13 (A) 3D CFM image of an HKUST‐1 single crystal obtained after an extended crystallization time. Bright planes represent planes of COOH dislocations. (B) 2D sections through the 3D reconstruction [22].

Scheme 11.1 Schematic representation of mCUS and superoxide formation upon activation of [Ba

2

(BTC)(NO

3

)]; M = Ba [35].

Figure 11.14 Structural model of defect nanoregions in UiO‐66(Hf) deduced from a set of complementary analytical methods. (a) Polyhedral representation of a single unit cell of UiO‐66. (b) Polyhedral representation of a single unit cell of the (ordered) defect structure. (c) Defect‐rich nanoregions are dispersed throughout a matrix of a defect‐free framework. (d) Atomistic model of defect nanoregions in UiO‐66(Hf). Di

fferent colors correspond to different orientations of the defect regions with respect to the bulk UiO‐66 (gray) [31].

Figure 11.15 QM‐/MM‐computed binding modes of CO. (a–d) QM/MM models of the local mixed‐valence defect Cu

II

/Cu

I

(BTC)

3

(PyDC) and energetically feasible binding modes for one to three adsorbed CO molecules (only the QM system is shown for clarity; Cu brown; C black; O red; N blue; H white) together with the computed (scaled) CO stretching normal‐mode frequencies (cm

−1

). (e) The defect (QM system) embedded in the MM environment [18].

Figure 11.16 Channel systems in dislocated zeolite A. For the dislocated system, the surface of the inaccessible volume viewed (a) down and (b) across the dislocation line; (c) the surface accessible volume with the central helix highlighted in blue [28].

Figure 11.17 Competitive adsorption modes of methanol on Zn

III

(as modeled on the {Zn‐Im

2

}cluster with one OH group on Zn), either molecular (a) or dissociation on Zn–OH pairs (b) [20].

Figure 11.18 (a) The stepwise dehydration of the most stable configuration of the cluster cornerstone; [78] (b) a cluster model of a dehydrated UiO‐66 cornerstone with one linker vacancy [9].

Figure 11.19 Conversion of TBCH over UiO‐66‐X and UiO‐66‐NO

2

‐X (X = equivalents of used TFA with respect to other reactants in MOF synthesis) versus time (toluene, 100%, TBCH/IPA/Zr

4+

 = 10 : 50 : 1) [32].

Scheme 11.2 Schematic representation of the proposed modified active site environment of MIL‐100(Fe) with additional Brønsted acid sites enhancing proton migration in the ring closure of citronellal [34].

Figure 11.20 Proposed mechanism for the structural breakdown of ZrMOFs in the presence of HCl (a), H

2

O (b), and NaOH (c). Carbon (gray), hydrogen (white), oxygen (red), and zirconium (light blue) atoms can be seen; hydrogen atom are omitted for clarity [84].

Chapter 12: MOFs as Heterogeneous Catalysts in Liquid Phase Reactions

Scheme 12.1 Synthesis of alcohols by MOF‐catalyzed ZnEt

2

(a) or ZnREt (b) addition to aldehydes, 1,2‐addition of Grignard reagent to carbonyl compounds (c), ring‐opening reaction of epoxides with alcohols (d) or amines (e), and Henry reaction between benzaldehyde and nitromethane (f).

Scheme 12.2 Friedel–Crafts acylation of aromatics (a), Diels–Alder cycloaddition (b), Meinwald rearrangement (c), Mukaiyama aldol reaction (d), and aldol reaction between aromatic aldehydes and ketones (e).

Scheme 12.3 Transesterification of ester by alcohol (a), carbonyl‐ene reaction (b), Mukaiyama aldol reaction to produce hydroxy ester (c), Knoevenagel condensation (d), aza‐Michael reaction (e), Beckmann rearrangement (f), and Friedländer reaction (g).

Scheme 12.4 Acetalization of benzaldehyde by trimethyl orthoformate (a) and glycerol (b), ketalization by ethylene glycol (c), and addition of benzyl alcohol to α,β‐unsaturated ketone (d).

Scheme 12.5 Isomerization of α‐pinene oxide (a), cyclization of citronellal to pulegol (b), cyclization of 3‐methylgeranial (c), and Prins condensation (d).

Scheme 12.6 Reaction scheme of Friedländer reaction; imination and aldolization paths are shown in upper and lower parts of the scheme.

Figure 12.1 Structure of transition states for the first and the second dehydration step of Friedländer reaction.

Figure12.2 Malononitrile interacting with an active site consisting of two paddlewheel units: (a) neutral malononitrile and (b) deprotonated malononitrile forming the defect site.

Chapter 13: Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis

Figure 13.1 Schematic representation of three major types of impregnation methods to encapsulate NPs into MOFs.

Figure 13.2 Organometallic compounds used in the chemical vapor deposition method

.

Figure 13.3 ADF‐STEM image of an MIL‐101 crystal loaded with Pt NPs by 40 ALD cycles. The arrows point out several examples: white arrows point to NPs at small cage positions (in projection) and the red arrow points to a nanoparticle at a large cage position.

Figure 13.4 The mechanism of formation of NPs into MOFs via assembly methods.

Figure 13.5 Entrapped Mn(III) salen complex in MIL‐101‐NH

2

using the bottle‐around‐the‐ship approach.

Figure 13.6 Schematic representation of the synthesis of Pt NPs in MIL‐101 using the double solvent approach.

Figure 13.7 Synthesis of Pd NPs in UiO‐67.

Figure 13.8 Schematic representation comparing the catalytic activities of Pt@MIL‐101 and Pt@Al

2

O

3

@SBA‐15 for the efficient and selective hydrogenation of benzaldehyde and nitrobenzenes.

Figure 13.9 Schematic representation of chiral modified Ru@ZIF‐8 nanocatalysts and their catalytic activity for asymmetric hydrogenation of acetophenone.

Figure 13.10 Schematic representation for the formation of Ru/MOF in Sc CO

2

‐methanol solution via interaction between active Ru NPs and carboxylate linker.

Figure 13.11 PdAg@MIL‐101 in the one‐pot nitroarene hydrogenation‐reductive amination of aldehydes to secondary arylamine.

Chapter 14: MOFs as Supports of Enzymes in Biocatalysis

Figure 14.1 (a) Representation of the 3D porous crystalline structure of UiO‐66. (b) Schematic drawing of the active sites of phosphotriesterase. (c) [Zr

6

O

4

(OH)

4

] clusters composing the nodes of UiO‐66. (d) Methanolysis reaction of methyl paraoxon (R = –CH

3

) and PNPDPP (R = phenyl). (e) Hydrolysis of methyl paraoxon.

Figure 14.2 Schematic representation of the three main routes to prepare MOF–enzyme systems.

Scheme 14.1 Esterification of lauric acid toward benzyl alcohol.

Scheme 14.2 Transesterification reactions of: (a) (±)‐1‐phenylethanol catalyzed by CALB–MOF; (b) and (c) vinyl acetate and vinyl laurate catalyzed by CalB@cap.

Scheme 14.3 Hydrolysis of D‐(−)‐salicin into glucose and salicylic alcohol by using β‐glucosidase‐NH

2

‐MIL‐53(Al) conjugate as catalyst.

Scheme 14.4 Hydrolysis of (

R

/

S

)‐1,2‐epoxyocatane toward (

R

)‐1,2‐octanediol catalyzed by SEH@UiO‐66‐NH

2

.

Scheme 14.5 Catalytic activity of OPAA@NU‐1003 and OPAA@PCN‐128y in the hydrolysis of (a) DFP and (b) Soman.

Scheme 14.6 Oxidation of 3,5‐di‐

tert

‐butylcatechol to 3,5‐di‐

tert

‐butylcyclohex‐4‐ene‐1,2‐dione catalyzed by MP‐11@Tb‐mesoMOF.

Scheme 14.7 Oxidation reactions of (a) phenylenediamine using HRP@PCN‐333(Al) and (b) 2,2′‐azinobis(3‐ethylbenzthiazoline‐6‐sulfonic acid) using Cyt

c

@PCN‐333(Al) and MP‐11@PCN‐333(Al).

Scheme 14.8 Co‐oxidation reaction of 4‐aminoantiprin and phenol catalyzed by HRP@POST‐66(Y)‐wt‐24h.

Scheme 14.9 Michael addition reaction of 4‐hydroxycoumarin and benzylideneacetone to warfarin catalyzed by PPL@MOFs.

Chapter 15: MOFs as Photocatalysts

Figure 15.1 Common molecular photocatalysts and inorganic semiconducting materials.

Scheme 15.1 Photocatalytic events occurring in a TiO

2

particle upon excitation with photons of appropriate wavelength. Legend: (1) Excitation; (2) charge migration to the surface; (3) molecular adsorption; (4) charge transfer.

Scheme 15.2 Illustration of different strategies to expand TiO

2

photoresponse to the visible region.

Scheme 15.3 Photocatalytic events occurring upon excitation of Au/TiO

2

using visible (a) or UV light (b).

Figure 15.2 (a) Ti

x

O

2−

y

(OH)

y

cluster incorporated within the cavities of zeolite Y and (b) its diffuse reflectance UV–Vis spectra at three increasing loadings (plots a, b and c).

Figure 15.3 (a) MIL‐125(Ti). View along (100). (b) MOF‐5 and (c) MIL‐101 showing supertetrahedra building units and how the assembly defines cages having pentagonal and hexagonal windows.

Figure 15.4 General photophysical step in which upon excitation of the linker, a single electron transfer for the linker as donor to the metal node as acceptor takes place.

Figure 15.5 UV–Vis transient absorption spectra of a N

2

‐purged aqueous solution of sodium terephthalate (1.1 × 10

−4

M) recorded 4 µs after 266 nm laser excitation before (⦁) and after (∆) the addition of an aqueous solution of Zn

2+

(2.6 × 10

−3

M). The inset shows the temporal profile of the signal monitored at 400 nm recorded for a N

2

‐purged aqueous solution of sodium terephthalate upon addition of increasing amounts of Zn

2+

from 0 to 2.6 × 10

−3

M.

Scheme 15.4 Typical quenching experiments

to assign transient absorption signals recorded for MOFs.

Scheme 15.5 Illustration cartoon of the two possibilities upon irradiation of MOFs. (a) Localized charge separation with lack of mobility and (b) behavior as semiconductor by migration of charge carriers throughout the crystal. Note that frequently one charge carrier migrates much faster than others.

Figure 15.6 (A) Photographs showing (a) TiO

2

(P‐25), (b) MOF‐5, (c) and SiO

2

(Aerosil) solid samples in contact with aqueous solutions of MVCl

2

, before (top) and after (bottom) irradiating with a solar simulator (525 W) through an AM1.5 filter for 10 min. (B) Photograph showing a dearated solution of NTP in (a) the absence and (b) the presence of MOF‐5 upon 355 nm laser irradiation.

Figure 15.7 Volume of H

2

evolved during the photocatalytic reactions using UiO‐66 (▪), UiO‐66/Pt (◽), UiO‐66(NH

2

) (⦁), and UiO‐66‐(NH

2

)/Pt (⚬).

Figure 15.8 (a) Tetracarboxylate porphyrinic linker used in the preparation of a mesostructured MOF and views of the resulting structure along the [001] (b), [100] (c), and [010] (d) directions.

Scheme 15.6 Oxidative condensation of alcohols and

o

‐aminothiophenols to produce 2‐substituted benzothiazoles.

Figure 15.9 Photodegradation curves of phenol (P) and 2,6‐di‐

tert

‐butylphenol (DTBP) obtained using MOF‐5 as a photocatalyst. (a) Curves correspond to photodegradation of 40 mg L

−1

of the pure species; (b) curves correspond to competitive photodegradation (irradiation of a mixture of mg L

−1

of both molecules).

List of Tables

Chapter 3: Synthesis of MOFs at the Industrial Scale

Table 3.1 General reported methods in patents to prepare MOFs.

Table 3.2 Surface area of HKUST‐1

under different concentrations and reaction times.

Table 3.3 Space‐time yield (STY)

of several MOF materials using different scaled‐up experimental conditions.

Chapter 5: Application of Metal–Organic Frameworks (MOFs) for CO

2

Separation

Table 5.1 CO

2

adsorption in MOFs

with open metal sites.

Table 5.2 Grafting amines into MOFs for CO

2

separation

.

Table 5.3 Summary of MOF composites with other materials and their CO

2

separation performance.

Chapter 7: MOFs for the Capture and Degradation of Chemical Warfare Agents

Table 7.1 Physicochemical parameters

of selected chemical warfare agents as well as immediately dangerous to life or health (IDLH)

a)

toxicity levels

.

Chapter 8: Membranes Based on MOFs

Table 8.1 Single‐gas selectivity of MOF/polymer mixed matrix membranes

.

Table 8.2 Mixture selectivity values of MOF/polymer mixed matrix membranes

.

Table 8.3 Summary of MOF thin‐film membranes for hydrogen separation.

Table 8.4 Summary of MOF thin‐film membranes for CO

2

separation.

Table 8.5 Summary of MOF thin‐film membranes for propylene separation.

Chapter 9: Composites of Metal–Organic Frameworks (MOFs): Synthesis and Applications in Separation and Catalysis

Table 9.1 Summary of MOF–CNT composite materials.

Table 9.2 Summary of MOF–GO composite materials.

Table 9.3 Summary of NP@MOFs with synthesis method

.

Table 9.4 Synthesized MO–MOFs composites and methods of their synthesis.

Table 9.5 Studies into

using MOF composites in catalysis.

Table 9.6 Summary of MOF composites usage as potential adsorbent.

Chapter 11: Role of Defects in Catalysis

Table 11.1 Summary on defective CNCs/MOFs for catalysis.

Chapter 13: Encapsulated Metallic Nanoparticles in Metal–Organic Frameworks: Toward Their Use in Catalysis

Table 13.1 CO oxidation activities

of common benchmark catalysts.

Table 13.2 Synthetic conditions and catalytic activities

of NPs@MOF for the gas phase oxidation of CO.

Table 13.3 Synthetic conditions and cat

alytic activities of NPs@MOF in liquid phase oxidation reactions.

Table 13.4 Synthetic conditions and catalytic activities

of NPs@MOF for the hydrogenation/reduction of substituted nitrobenzene.

Table 13.5 NPs@MOF that exhibited catalytic activity for the hydrogenation of olefins

.

Table 13.6 List of NPs@MOF that exhibited catalytic activity for the selective hydrogenation of cinnamaldehyde, 1,4‐butynediol, and phenol

.

Table 13.7 Direct hydrogenation of phenol

over the best heterogeneous nanocatalysts in liquid phase.

Table 13.8 List of NPs@MOF that exhibited catalytic activity for the H

2

formation from NH

3

BH

3

, formic acid, N

2

H

4

·H

2

O, and phenol derivatives.

Table 13.9 List of NPs@MOF that exhibited catalytic activity in C─C coupling reactions.

Table 13.10 List of NPs@MOF that exhibited catalytic activity in cascade reactions.

Chapter 14: MOFs as Supports of Enzymes in Biocatalysis

Table 14.1 List of biomimetic MOFs, including their chemical structure of their

organic ligand and metal precursors, and their respective catalytic reactions.

Table 14.2 List of enzyme–MOF systems, type of immobilization, and associated applications

.

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Metal-Organic Frameworks

Applications in Separations and Catalysis

Edited by Hermenegildo García and Sergio Navalón

Editors

Prof. Hermenegildo García

Technical University of Valencia

Av. de los Naranjos s/n

46022 Valencia

Spain

Dr. Sergio Navalón

Technical University of Valencia

C/Camino de Vera, s/n

46022 Valencia

Spain

Cover: The cover picture was kindly provided by Dr. Filipe A. Almeida Paz.

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Print ISBN: 978-3-527-34313-3

ePDF ISBN: 978-3-527-80912-7

ePub ISBN: 978-3-527-80910-3

Mobi ISBN: 978-3-527-80911-0

oBook ISBN: 978-3-527-80909-7

Cover Design Wiley

Preface

Metal‐organic frameworks (MOFs) in where metal nodes are coordinated to bi‐ or multipodal organic linkers defining a 3D lattice have emerged in the last decade as one of the most versatile type of materials. The large diversity of metals and organic linkers that can be used to obtain MOFs, combined with the possibility to apply some rules based on the consideration of the directionality of the coordination of around the building blocks to predict the resulting structure allows certain level of design in MOFs that is not possible for other related porous crystalline materials, such as zeolites and porous aluminophosphates.

Other structural features that are also characteristics of most MOFs are a large surface area, mostly internal, with high pore volume and comparatively large pore sizes. It has to be considered that MOFs are among the materials with the largest surface area, not uncommonly above 1000 m2 g−1, with the lowest framework density, meaning that the mass divided by the volume of the unit cell is very often the minimum among all the materials, reflecting the large void space of MOFs.

In addition, frequently, the coordination sphere of the metal nodes contains some exchangeable ligands occupied by solvent molecules that are not compromised with the lattice and can be involved in adsorption phenomena. The combination of all these features, that is, large percentage of metals in their composition, open coordination positions, high surface area and porosity, together with reproducible synthetic procedures make MOFs promising materials for a series of applications. In the present book, we have focused on the application of MOFs as adsorbents and solid catalysts. Heterogeneous catalysis takes place after adsorption of substrates and/or reagents on the active sites and, therefore, adsorption is an elementary step that can lead to the subsequent transformation of the adsorbate. The use of MOFs as adsorbents and heterogeneous catalysts is currently progressing at a fast pace, since research on these fields is very active due to the large possibilities that MOFs offer in terms of the choice of metal, topology and dimensions of the structure, possibility to incorporate guests and post‐synthetic modification of the structure by organic synthesis or exchange.

The present book contains a collection of 15 chapters written by authors that have contributed to the development of their respective field. The book tries to provide a balanced coverage of the various aspects related to the use of MOFs as adsorbents and catalysts. The two first chapters deal with the synthesis of robust MOFs or post‐synthetic modification of the pristine material. One of the strongest criticisms against the large scale application of MOFs in adsorption and catalysis is their lack of structural stability. However, while not all MOFs are certainly stable upon heating in certain solvents or in the present of reagents, it has been shown that there are certain MOFs, such as MIL‐100 and UiO‐66, that are structurally robust in a wide range of treatments and they can stand most of the conditions required in gas adsorption, separation and liquid‐phase reactions. Considering the importance that MOFs can have in these large scale applications, Chapter 3 summarizes the synthesis of MOFs at industrial scale, indicating the differences of these commercially available MOFs with respect to samples prepared at smaller scale. Besides 3D MOFs, MOFs forming films or 2D structures that can subsequently by pillared and transformed into 3D materials are growing in importance for those uses that require solids with this particular morphology and they are described in Chapter 4.

Chapters 5–8 deal with the use of MOFs as adsorbents, including application of these materials in CO2 gas separation, methane storage, and capture and degradation of chemical warfare agents. These three topics are currently attracting considerable attention in the context of decrease of atmospheric CO2 emissions, development of CO2 circular economy, better use of less‐polluting fossil fuels and protection against toxic chemicals. In fact, the tunability of MOF structure and the possibility that these solids offer of post‐synthetic modification allows the control of a large number of critical parameters that can lead to strong CO2 and CH4